Oxyalkylated condensates



June 1, 1965 M. DE GROOTE ETAL OXYALKYLATED CONDENSATES Original Filed May 8, 1958 FIGURE l BINARY REACTION PRODUCT FOR OXYETHYLATION 2 Sheets-Sheet 1 I00 CON DENSATE I BINARY REACTION PRODUCT FOR OXYPROPYLATION I00 CaH4O MELVIN DE GROOTE KWAN-TING SHEN INVENTORS June 1, 1965 M. DE GROOTE ETAL 3,186,951

OXYALKYLATED CONDENSATES Original Filed May 8, 1958 2 Sheets-Sheet 2 BUTYLENE OXIDE l00% CONDENSATE II ETHYLENE OXIDE FIGURE 2 MELVIN DE GROOTE KWAN-TING SHEN INVENTORS tates ate This application is a division of Serial No. 734,000 filed May 8, 1958, now U.S. Patent No. 3,128,314, issued April 7, 1964.

This invention relates to oxyalkylated hydrocarbon carbohydrate condensates prepared by reacting an oxyalkylation agent with a condensate of a hydrocarbon with a carbohydrate and materials closely related to carbohydrates (also referred to as condensates), particularly those condensates formed by reacting said carbohydrates with a hydrocarbon in the presence of a Friedel-Crafts catalyst, preferably hydrogen fluoride. More particularly this invention relates to oxyalkylated hydrocarboncarbohydrate condensates prepared by treating an oxyalkylation agent with a condensate of a hydrocarbon and a simple sugar, their desoxy and omega-carboxy derivatives, compound sugars or oligosaccharides and polysaccharides, particularly those formed by reacting said sugars with an aromatic hydrocarbon in the presence of a Friedel-Crafts catalyst, preferably hydrogen fluoride. This invention also relates to process or procedures for employing these condensates for preventing, breaking or resolving emulsions of the water-in-oil type, and particularly petroleum emulsions as well as in various other arts and industries.

More specifically, the present invention is concerned with oxyalkylated condensates derived from the condensates, propylene oxide and ethylene oxide in such weight proportions so the average Composition in terms of initial reactants lies approximately within the trapezoid of the accompanying FIG. I of which the minimum condensate content is at least 1.75% and which trapezoid is identified by the fact that its area lies within the straight lines connecting A, B, F, B. Our preference is to use the compositions which represent less than one-half of this total area, to wit, the smaller trapezoid A, B, D, C.

It is immaterial as to whether one reacts the condensates with propylene oxide first and then with ethylene oxide, or with ethylene oxide and then with propylene oxide; or for that matter, one may employ a mixture of the two oxides; or, if desired, one may add a small amount of ethylene oxide, then propylene oxide, and then more ethylene oxide.

hlddfifi ?atented June 1, i65

ice

HYDROCARBON-CARBOHYDRATE CONDENSATES The oxyalkylated products of this invention are prepared from water insoluble condensation products and also water soluble condensation products formed by reacting hydrocarbons with carbohydrates and related substances in the presence of a hydrogen fluoride catalyst. These condensation reactions may be carried out in steel equipment or other suitable apparatus lined with silver, copper, and certain alloys such as Monel metal and the like. This treatment may be effected at, temperatures of from about to about 100 C., and preferably at temperatures of from about 10 to about C. The pressure at which the reaction is carried out willvary with the reaction temperature used, the mol fractions of reactants and hydrogen fluoride catalyst present, and the volume of the particular reactor utilized. While many of the condensation reactions are carried out at substantially atmospheric pressure, it may be desirable in certain instances and with certain reactants to carry out the the reaction'at pressures up to 100 atmospheres or more. It is convenient in most instances to operate the equipment utilized at the pressure generated by the reaction mixture and the catalystcontained therein.

Hydrocarbons which may be used as starting materials in preparing'the condensates include isoalkanes or isoparaflinic hydrocarbons, alkenes or olefinic hydrocarbons,

.alkynes or acetylenic hydrocarbons, alkadienes, aromatic Referring to the hereto attached FIG. I, it is simplified in by noting that one may react the condensate with enough ethylene oxide so the binary reaction product falls Within the mixture identified by the line CC-DD on the extremity of the graph which shows combinations derived solely from the condensate and ethylene oxide. After obtaining such binary reaction product it can then be reacted with propylene oxide so as to bring it Within the area of the trapezoid A, B, F, E, or preferably within the smaller trapezoid A, B, D, C.

Similarly, one can produce a binary reaction product from the condensate and propylene oxide as identified by the comparable line AA-BB and subject this reaction product to oxyethylation so as to bring the composition within the area of the trapezoid and preferably within the area of the small trapezoid A, B, D, C.

Another advantageous aspect of the present invention is concerned with oxyalkylated condensates derived from the condensates, ethylene oxide and butylene oxide in such weight proportions so the average composition of hydrocarbons, hydrocarbons with condensed benzene rings, cyclanes or cycloparaflinic hydrocarbons and terpenes.

Typical utilizable alkanes include isobutane, Z-methylbutane, 2,3-dimethylpropane, Z-methylpentane, 3-methylpentane, 2,3-dimethylbutane, Z-methylhexane, 3-methylhexane, 2,3-dimethylpentane, 2,4-dimethylpentane, 2,2,3- trimethylbutane, Z-methylheptane, 3-methylheptane, 4- methylheptane, 2,3-dirnethylhexane, 2,4-dimethylhexane, 2,5 -dimethylhexane, 2,2,3-trimethylpentane, 2,2,4-trimethylpentane, 2,3,3-trimethylpentane, isononanes, isodecanes, isoundecanes, isododecanes, etc.

Suitable utilizable alkene hydrocarbons include ethylene, propylene, l-butene, Z-butene, isobutylene, pentenes, hexenes, heptenes, octenes, nonenes, decenes, undecenes, dodecenes, etc. High molecular weight polyolefinic hydrocarbons such as those recovered from hydrogen fluoride catalysts used to catalyze the polymerization of olefins, or to catalyze the alkylation of isoparaflinic hydrocarbons with olefins, are also Utilizable in the process of the present invention.

Utilizable alkyne hyr-ocarbons include acetylene, methyl acetylene, ethylacetylene, propylacetylene, butylacetylene, etc., dimethylacetylene, methylethylacetylene,

diethylacetylene, ethyl-propylacetylene, etc. These acetylenic hydrocarbons may also contain aryl and alkaryl substituents such as phenylacetylene, tolylacetylene, etc.,

Suitable utilizable alkadiene hydrocarbons include propadiene or allene, derivatives of allene, butadiene, 2- methylbutadiene or isoprene, etc. I

Suitable utilizable aromatic hydrocarbons include ben Zene, toluene, o-xylene, m-xylene, p-xylene, ethylben'zene, 1,2,3 -trirnethylbenzene,1,2,4 trimethylbenzene, 1,3,5-

trime-thylbenzene or mesitylene, ortho ethyltoluene, metaethyltoluene, p-ethyltoluene, n-propyl-benzene, isopropylbenzene or cumene, etc. Higher molecular weight alkyl-aromatic hydrocarbons are also suitable 'such 'as those produced by the alkylation of aromatic hydrocarbons with olefinic polymers. Such products are referred to in the art as .alkylate, and include hexylbenzene, hexyltoluene, nonylbenzene, nonyltoluene, dodecylbenzene, dodecyltoluene, etc. Very often alkylate is obtained as a high boiling fraction in which case the alkyl group attached to the aromatic hydrocarbon varies in size from C9 C13. 7 i

Other suitable utlizable aromatic hydrocarbons include those containing an unsaturated side chain such as styrene, vinyl-toluene, etc.

Other suitable utilizable aromatic hydrocarbons include those with two or more 'aryl groups such as diphenyl, diphenylmethane, triphenylmethane, fluorene, stilbene, etc. Examples of suitable utilizable hydrocarbons which contain condensed benzene rings include naphthalene, anthracene, phenanthrene, naphtharene, rubrene etc.

In addition, aromatic hydrocarbon derivatives which may be used as starting materials in preparing the condensate include aroma-tic nitro compounds, aromatic sulfonic acids, aromatic amines, phenols, aromatic halogen compounds, aromatic carboxylic acids, aromatic aldehyde and aromatic ketones.

toluene, p-bromotoluene, o-bromo-anisole, p-bromo-dimethylaniline, o dichlorobenzene,

' nilic acid, m-aminobenzoic acid, p-aminobenzoic acid, etc.

Utilizable derivatives of' benzoic acid include methylbenzoate, benzoic anhydride, benzoyl chloride, perbenzoic Typical utilizable aromatic nitro compounds include Suitable utilizable aromatic sulfonic acids include ben zene sulfonic acid, o-toly1 sulfonic acid, m-tolyl sulfonic acid, p-tolyl sulfonic acid, various xylene sulfonic acids, dodecylbenzene sulfonic acids, dodecyl toluene sulfonic acids, etc. Acid chlorides formed by the reaction of aromatic acids with phosphorus halides are also utilizable. The esters, sulfonamides, and chloroamides formed from aromatic sulfonic acids may also .be used as well as nitriles, and'sulfinic acids.

Utilizable aromatic amines include aniline, methylaniline, dimethylaniline, diethylaniline, o-toluidine, m-

-toludidine, p-toluidine, o-nitroaniline, m-nitroaniline,'p-

nitroaniline, 2,4-dinitroaniline, o-phenylene diamine, mphenylene diamine, p-phenylene diamine, o-anisidine, p-

anisidine, p-phenetidine, o-chloroaniline, m-chloroaniline,

p-chloroaniline, p-bromoaniline, 2,4,6-trichloroaniline, 2,4,6 tribromoaniline, diphenylamine, triphenylamine, benzylidine, o-tolidine, o-diani sidine, 'etc. Theacid salts and acetyl derivatives of the various aromatic amines may also be utilized.

Typical utilizable hydroxy aromatic hydrocarbons include phenol, o-cresol, m-cresol, p-cresol, o-chlorophenol, p-chlorophenol, m-chlorophenol, p-bromophenol, 2,4,6-

-trichlorophenol, 2,4,6-tribromophenol, o-nitrophenol, m- -nitrophenol, p-nitrophenol, 2,4-dinitropl1enol, guaiacol anol, eugenol, isoeugenol, saligenin, carvacrol, thymol, o-hydroxyacetophenone, p-hydroxya cetophenone, o-hydroXydiphenyl, p-hydroxydiphenyl, o-cyclohexylphenol, p-cyclohexylphenol, catechol, resorcinol, hydro quinone, pyrogallol, hydroxy-hydroquinone, phloroglucinol, o-aminophenol, m-aminoph'enol, p-aminophenol, etc.

Aromatic halogen compounds ,utilizablein' the scope of this invention include fluorobenzene, chloro'benzene, bromobenzene, iodobenzene, o-chlorotoluene, rn-chloro- 'toluene, p-chlorotoluene, o-bromotoluene, mbrornoacid, dibenzoyl peroxide, benzamide, benzanilide, benzhydrazide, etc. Utilizable polybasic acids and derivatives include phthalicacid, phthalic anhydride, isophthalic acid, te'rephthalic acid, hemellitic acid, trimellitic acid, trimesic acid, prehnitic acid, mellophanic acid, pyromellitic acid, benzene pentacarboxylic acid, mellitic acid, diphenic acid, etc; Also, benzene derivatives with acidic side chain may be used; for example, phenyl acetic acid, hydrocinnamic acid, omega-phenylbutyric acid, delta-phenyl-n-valeric acid, omega-phenyl-n-caproic acid, cinnamic acid, phenylpropionic acid, homophthalic acid, o-phenylene-diacetic acid, m-phenylenediacetic acid, p-phenylenc-diacetic acid,

o-phenylene-acetic-B-propionic acid, etc.

Utilizable aromatic aldehydes and ketones include benzaldehyde, m-tolualdehyde, p-tolualdehyde, ochlorobenzaldehyde, p chlorobenzaldehyde, o nitrobenzaldehyde, m-nitrobenzaldheyde, p-nitrobenzaldehyde, o-aminobenzaldeh'yde, p aminobenzaldehyde, salicylaldehyde, m-hydroxybenzaldehyde, p-hydroxyhenzaldehyde, o-methoxybenzaldehyde, anisaldehyde, p-dimethylaminobenzaldehyde, 2,6-dichlorobenzaldehyde, vanillin, acetophenone, propiophenone, benzophenone, fluoroacetophenone,

p-dimethylaminobenzophenone, etc. 7

Suitable utilizable cycloalkane hydrocarbons include alkylcycl'oalkanes such as methylcyclopropane, methyl- 'phenylcyclohexane, formed by the loss of one molecule of hydrogen to pro- .decoses. 'saccharides, and tetrasaccharides. *clude polysaccharides com-posed of only one type of sugar cyclobutane, methylcyclopentane, methylcyclohexane, etc.,

aryl substituted cycloalkanes', such asphenylcyclopentane, etc. Derivatives of cycloalkanes duce cycloalkenes or cycloalkanes containing an unsaturated side chain are also Within the scope of the present invention, as are diolefinic cycloalkanes such as cyclopentadiene, etc.

Suitable utilizable terpenic hydrocarbons'include menthane, limonene, thujanc, carane, pinane, camphane, sabi- 'nene, carene, alpha-pinene, beta-pinene, etc.

Carbohydrates which are condensed with hydrocarbons include simple sugars, their desoxy and omega-carboxy derivatives, compound sugars or oligosaccharides, and polysaccharides. Simple sugars include dioses, trioses, tetroses, pentoses, hexoses, heptoses, octoses, nonoses, and

Compound sugars include disaccharides, tri- Polysaccharides inresidue, polysaccharides composed of more than one type of sugar unit, polysaccharides composed of one type of uronic acid'unit, i.e., vpolyuronides, polysaccharides com prised of aldose (pentose orhexose) and uronic acid units, polysaccharides containing hexose units esterified with an inorganic acid, and. polysaccharides containing amino sugar units.

' Utilizable simple sugars include the diose, glycoalde- V hyde, trioses,,such as glyceraldehyde and s-dihydroxyacetone, .tetroses, such as erythrose, threose, erythrulose,

andapiose; the pentoses such as arabincse, Xylose, ribcse, .lyxose, rhamnose (-a desoxyhexose), fucose (a 'desoxyhexose), rhodeose, digitalose, and ketoxylose; the hexoses,

such as mannose, glucose, idose, gulose, gallactose, t-alose, allose, alt-rose, fructose, sorbose, tagatose, and psicose; heptoses such as glucoheptose, manneheptose, galactohextose, sedohe tose, mannoketoheptose, glucoheptulose, and perseulose; octoses such as glucooctose, mannooctose, and gallactooctose; nonoses such as glucononose, and mannononose; and decoses such as .glucodecose. Desoxy derivatives of simple sugars are formed by the replacement of a hydroxyl substituent in a sugar with hydrogen thereby forming a methyl or methylene linkage. The desoxypentoses and desoxyhexoses are the most commonly occurring of such compounds. The omega-carboxy derivatives of simple sugars, which are suitable in the process of the present invention include tartronic semialdehyde or its tautomer, hydroxypyruvic acid, a,ydihydroxyacetoacetic acid, threuronic acid, 4-keto-2,3,5, trihydroxypentanoic acid, xyluronic acid, S-keto-hexanoic acids such as S-lreto-allonic acid, S-keto-gluconic acid, 5- ketomannonic acid, S-ketogulonic acid, and S-keto-gallactonic acid, uronic acids such as glucur-onic acid, mannuronic acid and gallacturonic acid, and the S-ket-oheptanoic acids. The simple sugars and their omega-carboxy derivatives, as starting materials for the process of this invention, may be represented by the following general formula:

A 3:0 (Hot ni)n in which A:H and CH OH, 11:an integer from 1 to about 12 or so, and B:H, CH OH, and COOH. As an example of the utility of this general formula when A:H, 11:1, and B:H, the compound is glycolaldehyde; when A:H, 11:1, and B:CH O-H, the compound is glyceraldehyde; when A:H, 11:1 and B:COOH, the compound is tartaronic semialdehyde, a tautomer of hydroxypyruvic acid; when A:CH OH, 11:1, and B:H, the compound is s-dihydroxyacetone; when A:CH OH, 11:1, and B:CH C H, the compound is erythrulose; when 11:1, and B:COOi-l, the compound is a,y-dihydroxyacetic acid; when A:H, 11:2, and B:CH OH, the com-pound is threuronic acid; when A:CH OH, 11:2, and B:CH OH, the compound is riboketose, or xyloketose; when A:CH OH, 11:2, and B:C()OH, the compound is 4--keto-2,3,S-trihydroxypentanoic acid; when A:H, 11:3, and B:CH OH, the compound is ribose, arabinose, xylose, or lyxose; when A:H, 11:3, and B:COOH, the compound is xyluronic acid; when A:CH OH, rr:3, and B:"H OH, the compound is psicose, fructose, sorbose, or tagatose; when A:C-H OH, 11:3, and B:COOH, the compound is S-ketohexanoic acid; when A:H, 11:4, and B:CH OH, the compound is allose, altrose, glucose, mannose, gulose, idose, gallactose, or talose; when A:H, 11:4, .and B:COOH, the compound is a uronic acid; when A:H 0H, 11:4, and B:VH OH, the compounds are heptoses; and when A:CH OH, 11:4, and B:COOH, the compounds are 6-ketoheptanoi-c acids.

The utilizable oligosaccharides or compound sugars include disaccharides such as the pentose-hexose saccharides including glucoapios'e, vicianose, and primeverose; the methylpentose-hexose saccharides including glycorhamnoside, and rutinose; and the dihexoses such as turanose, maltose, lactose, cellobiose, gentiobiose, melibiose, sucrose, and trehalose. Other compound sugars are represented by trisaccharides such as the methylpentosehexose saccharides including rhamminose, and robinose; the trihexose saccharides such as mannotriose, and the trihexoses including rafiinose, melezitose, and gentianose. An example of a suitable tetrasaccharide is stachyose.

Various polysaccharides are also utilizable in'the process of the present invention. These polysaccharides include pentosans such as araban, methylpentosans, such as in osan, the hexosans such as starch, cellulose l co en,

inulin, mannan, galactan, lichenin, levan, dextran'and laminarin. All of the above polysaccharides are composed of one type ofsugar residue. Other polysaccharides which are composed of more than one type of sugar unit such as the pentosans, like araboxylan and the hexosans like galacto-mannan may be used. Other utilizable polysaccharides are represented by those composed of urosic acid units such as pectic acid and alginic acid, those composed of :aldose pentose or hexose) and uronic acid units such as gum arabic, damson gum, gum tragacanth, linseed mucilage, pectins, and those containing hexose units esterified with an inorganic acid such as certain seaweed polysaccharides like agar.

The hydrogen fluoride catalyst which is used in preparing the condensate may be used in anhydrous form or diluted with water to makea hydrofluoric acid of the de sired concentration. The hydrofluoric acid may also be further diluted with various inert diluents when it is desirable to operate the process of this invention with low hydrogen fluoride concentrations. Suitable inert diluents include normal parafiinic hydrocarbons such as propane, n-butane, n-pentane, n-hexane, etc., and perfluoro derivatives of n-paraffinic hydrocarbons such as perfiuoropro pane, perfluoro-n-butane, perfiuoro-n-pentane, perfluoro-nhexane, etc. Other'suita'ble diluents in these classes are apparent to one skilled in the art. For example, cycloparaffins as cyclopentane and cyclohexane may be used. In some instances, hydrofluoric acid of from about to about HP concentration is desirable, and in some other instances it is most desirable to use anhydrous hydrogen fiuoride as the catalyst.

, This process may be carried out by slowly adding a hydrogen fluoride catalyst to a stirred mixture of the hydrocarbon and carbohydrate or related material'being subjected to reaction while maintaining the reaction temperature at from about 40 to about 100 C. By suitable cooling and/or heating means it is often advisable or desirable to commingle the reactants and catalyst at a relatively low temperature such as from about 80 to about 30 C. and then to permit the reaction mixture to warm gradually while the reactants and catalyst are stirred by suitable means such as a motor driven stirrer or other adequate mixing equipment. After the reaction has reached the desired degree of completion, the hydrogen fluoride catalyst is removed from the reaction mixture by distillation at atmospheric or lower pressures or by passing an inert gas through the reaction mixture While maintaining it atrelatively low temperature. Also the entire reaction mixture and catalyst may be mixed with water or may be added to ice in order to quench the activity of the hydrogen fluoride catalyst and permit separation of the organic reaction products and unreacted starting materials from the catalyst. The organic reaction products may also be separated from aqueous hydrogen fluoride by means of an organic solvent such as ether in which some of the organic material may be dissolved. Further methods of isolating the reaction products are illustrated in the examples. Thus the product formed by reacting tolu ene with glucose or cellulose in the presence of substantially anhydrous hydrogen fluoride at 30 C. is separated into an ether soluble and water insoluble product and an ether insoluble and water-soluble product.

Thus, these materials are the oxyalkylated reaction products of carbohydrates including simple sugars, their derivatives, compound sugars, and polysaccharides with hydrocarbons such'as isoparaflins, olefins, aromatics, naphthenes, terpenes, etc., using as a catalyst hydrogen fluoride. The type of product is markedly aflectedby the length of time that the reactants are in-contact with the hydrogen fluoride catalyst as well as the temperature of reaction.

While hydrogen fluoride isthe catalyst preferred for this process, the invention may also be carried out in some instances in the presence of other catalysts including catalysts of the Friedel-Crafts type, particularly aluminum 7 chloride, as such or modified by addition thereto of an alcohol, ether,'ester, nitroparaflin, alkyl halide, and the like. Mixtures of boron fluoride and hydrogen fluoride may also be employed. In some cases, fiuoro acids are also active in this process, including'fiuorosulfonic acid, fluorophosphoric acids, hydroxyborofiuoric acid and the like.

These hydrocarbon-carbohydrate condensates are known compounds and have been described in the following publications:

U.S. Patents 2,798,097, 2,798,098, 2,798,099, and 2,798,100; in Chemical and Engineering News, September 16, 1957; and in a paper presented by Carl B. Linn at the National Meeting of the American Chemical Society, Petroleurn Division, New York city, September 8-13, 1957, entitled The Catalyzed Condensation of Aromatic Compounds with Carbohydrates, a copy of which is available from Universal Oil Products Company. These patents and publications are by reference hereby incorporated in' the present application.

OXYALKYLATED I-IYDROCARBON-CARBO- HY DRATE CONDENSATES chlorohydrin, methylglycide, glycide, etc. Substituted alkylene oxides can also be employed, for example, styrene oxide, and the like. They can be oxyalkylated with mixed alkylene oxides to form random polyalkylene oxide moieties, AABABBAAAB, or they can be oxyalkylated to form block polyalkylene oxide moieties,

BBBAAABBBAAABBB wherein A is the unit derived from one alkylene oxide, for example, ethylene oxide, and B is the unit of a second alkylene oxide, for example, propylene oxide. These also include ter-polyalkylene oxide or higher moieties, where 3 or more alkylene oxides are reacted in a random or blockwise pattern.

Specifically, these condensates canbe oxyalkylated in the manner heretofore employed in oxyalkylated sucrose as disclosed in U.S. Patent 2,652,394 except that unlike sucrose, which forms a slurry in a solvent such as xylene, the present condensates are generally soluble in xylene. In 'view of the fact that oxyalkylation procedures are so well known, for the sake of brevity, particular attention is directed to the various US. patents which describe typical oxyalkylation procedure, for example, US. Patents 2,652,394, 2,792,371, 2,499,368 and the technical bulletin entitled Ethylene Oxide which has-been distributed. by the Jefierson Chemical Company of Houston, Texas. Note also the extensive bibliography in this bulletin and the large number of patents which deal with oxyalkylat-ion V procedure. I

. Depending on the particular application desired, one -may combine a' larger proportion or a smaller proportion of alkylene oxide to the condensate. Thus, 'the molar ratios of alkylene oxide to condensate can range, for example, from 1:1 weight ratios to ratios of from 1:200 more, but preferably 1:80. By proper control hydrophilic properies can be imparted to the condensate. As is well known, oxyalkylations are conducted under a wide variety of conditions, both atlow and high'pressure, at low and high temperature, in .both the presence or absence or catalysts, solvents, etc. 'Eor instance, oxyalkylations can be carried out at temperatures of 70-200? C. and pressures of from 10-200 p.s.i. and times of from minutes to several days; Preferably, oxyalkylations are'carried out at'80,l30 C.-at1030 p.s.i., f g

Because of the polyfunctional ability of. the oxyalkyla- .tion susceptible material cogeneric .mixtures are formed rather than single chemical compounds. For example,

the condensate formed from glucose,

has five oxyalkylation susceptible OH groups. Furthermore, where the hydrocarbon has additional oxyalkylation susceptible groups, further permutations are introduced.

Thus, where one oxyalkylates condensates such as Hi-OH Hod-H HCOH HAD-OH H OH 7 there are oxyalkylation-susceptible phenolic groups as well as the five oxyalkylation susceptible aliphatic (3H groups. Where other oxyalkylation-susceptible groups are present in the molecule such as amino groups, carboxylate groups, etc., additional reaction centers are introduced. Since monofunctional alcohols are known to oxyalkylate statistically to form homologous compounds having an average degree of oxyalkylation, this factor would, of course, be mutiplied many times in the case of the polyfunctional compound of this invention. Thus, the compositions of this invention are cogeneric mixtures best described by the method of preparation. I

The following examples are presented for purposes of illustration. For purposes of illustrating the invention the following two condensates are employed.

'COndensate l.-1-deoxy-1, l-di-(o-xylyl) D glucitol (made from o-xy1ene and starch).

- Condensate II.1-deoxy-1, 1-.di- (p-hydroxyphenyl) and-condensate 11.

' Example 1 The reaction vessel employed is a stainless steel auto- .clave with the usual devices for heating, heat control,

. stirrer, inlet, outlet, etc., which is conventional in this required to add the propylene oxide is two hours.

type of apparatus. The capacity is approximately 4 liters. .Thestirrer is operated at a speed of approximately 250 .r.p'.m. There is charged into the autoclave 500 grams of condensate I, 300 grams of xylene, and. 15 grams of sodium methylate. The autoclave is sealed, swept with nitrogen gas and stirring started immediately and heat applied. The temperature is allowed to rise to approximately C. At this particular time the addition of propylene oxide is started. Propylene oxide is added continuously at such speed that it is absorbed by the reaction as added. The

amount added in this operation is 1500 grams. The time During this period the temperature is maintained at 138 to 150? C, using cooling water through the, inner coils when necessary and otherwise applying-heat if required. The

maximum pressure during the reaction is 52 pounds per [square inch. Ignoring the xylene and sodium methylate and considering only condensate I foriconvenience, the

:resultant product represents 3 .partsjby weight of propylene oxide to one part by weight of the condensate 'I. The

xylene presentrepresents approximately .6 part by weight.

Example 2 The reaction mass of Example 1 is transferred to a larger autoclave (capacity 15 liters). Without adding any more solvent or any more xylene the procedure is repeated so as to add another 1500 grams of propylene oxide under substantially the same operating conditions but requiring about 3%. hours for the addition. At the end of this step the ratio represented approximately 6 to 1 (ratio propylene oxide to condensate 1).

Example 3 In a third step, instead of adding 1500 grams of propylene oxide to the product of Example 1, 1625 grams are added. The reaction slows up and requires approximately hours, using the same operating temperatures and pressures. The ratio at the end of the third step is 9.25 parts by weight of propylene oxide per weight of condensate I.

Example 4 At the end of the third step (Example 3) the autoclave is opened and an additional 5 grams of sodium methylate added, the autoclave flushed out as before, and the fourth and final oxyalkylation completed, using 1625 grams of propylene oxide, and the oxyalkylation is complete within 3 /2 hours using the same temperature range and. pressure as previously. At the end of the reaction the product represents approximately 12.5 parts of propylene oxide by weight to one part of condensate I.

Having obtained oxpropylated condensates, the products are subjected to oxyethylation in a manner comparable to the oxyethylation of triethanolamines, or for that matter, in the same way that oxypropylated sucrose is subjected to oxyethylation in the manner described in US. Patent No. 2,652,394, dated September 15, 1953, to De Groote. Indeed, the procedure is comparatively simple for the reason that one is working with a liquid and also that ethylene oxide is more reactive than propylene oxide. As a result, using the same amount of catalyst one can oxyethylate more rapidly and usually at a lower pressure.

The same procedure using condensate I in xylene is employed in connection with ethylene oxide and the same mixture on a percentage basis is obtained as in the above examples Where propylene oxide and condensate I are used. Similarly corresponding examples with condensate limits. In such instances, of course, the oxyalkylation may be described as random oxyalkylation insofar that one cannot determine the exact location of the propylene oxide or ethylene oxide groups. In such instances the procedure again is identically the same as previously described.

Actually, the condensate at times may contain a trace of moisture. Our preference is to prepare the mixture with an excess of xylene and distill off a part of the xylene so as to remove any trace of water and then flush out the mass with nitrogen. Even so, there may be a few tenths of a percent of moisture remain although at times examination indicates at the most it is merely a trace.

As previously pointed out the simplest procedure of all is to prepare a binary reaction product of ethylene oxide on the one hand or the condensate and propylene oxide on the other hand, and react with the other oxide. Note line CCDD which indicates that in the binary reaction product obtained from the condensate and ethylene oxide one employs approximately 66.6% to 96.5% of ethylene oxide and approximately 3.5% to 33.4% of the condensate.

Similarly, if one refers to the line AA-BB it means one would employ from 1.95% of the condensate up to 14.3% of the condensate and from 85.7% of propylene oxide up to 98.05% of propylene oxide.

In other operations we proceed as follows: Mix the condensate with an aromatic petroleum solvent and with powdered caustic soda. Stir this mixture at 125 to 130 C. for a short period of time, approximately one-half hour, flush out with nitrogen, and then subject to vacuum so as to eliminate any moisture. Start to oxypropylate and continue until oxypropylation completes and then immediately follow with ethylene oxide. In these examples the amount of materials used is indicated in pounds and in each instance, of course, a suitable size autoclave is used. Although the oxyalkylation starts under vacuum the maximum pressure at any time is about 10 to 15 pounds. used and stirring speed is approximately 350 r.p.m. These data covering nine oxyalkylations are included in Table I, immediately following. The time periods are shown. Incidently, we can repeat these same operations using ethylene oxide first and then propylene oxide and we can also mix the two oxides and complete the same nine oxyalkylations under substantially the same con- II are also carried out. ditions.

TABLE I High boiling Maximum Ex. No. Condensate aromatic Caustic Propylene Ethylene Time, Temp, press,

I petroleum soda, lbs. oxide, lbs. oxide, lbs. hrs; 0. lbs. per

solvent, i sq. n1.

lbs.

In the preceding procedures one oxide is added and then the other. One need not follow thisprocedure. The two oxides can be mixed together in suitable proportions and subsequently subjected to joint oxyalkylation so as to obtain products coming within the specified Referring again to the ratio of the inital'reactants based on the trapezoid in attached drawing, we have calculated the percentage of the three initial'reactants for the points A, B, C, D, E, and F, and Nos. 1 through 14, inclusive.

. We have also calculated initial binary mixtures corre- An efficient agitating device is i 3,186,951 1 1 spending in essence to the lines CC--DD and AA-BB, all of which appears in self-explanatory form in Table II, immediately following.

angles and a rectangle. The rectangle then obviously can be divided into three portions of the same size by drawing two additional lines, all of which is shown in the in two places, thus dividing the trapezoid into two tritime required to add the butylene oxide is two hou rs;

TABLE II Tertiary mgxture, percent Binary intermediate mixtures, percent Points on am boundary of area Conden- Pro- Eth- Conden- Pro- Oonden- Ethsate I pylene ylene sate I pylene sate I ylene oxide oxide oxide oxide As previously pointed out, the oxyalkylation process drawing on a larger scale and in dotted lines only. In the .j has been described in the literature and is described also hereto attached claims the area within the upper apex of l in detail above. All one need do is employ such conventhe trapezoid refers to the area within such upper tritional oxyalkylation procedures to obtain products cOrangle; the area within the lower apex of the trapezoid reresponding to the compositions as defined. Attentionis fers to such lower triangle. The area in the center of the again directed to the fact that one need not add the entire trapezoid refers to the area defined by the middle recamount of either oxide at one time but that a small pOrtangle. The area of one rectangle is defined by being betion of one could be added and then another small por tween the upper apex and the center rectangle, and the non of the other, and the processrepeated. other by being between the lower apex and the center .For purpose of illustration We can pr pare xampl rectangle, all of which is perfectly plain by reference to 1 three different y cofrespontimg t0 the COIIIPPSIUOIIS the drawing. An attempt to draw additional lines and n the g' In the fir n s P ps 1 1 oxide and .to number them in the same trapezoid, 'A, B, D, 0, would ethylene oxide are mixed; thl s r s ls lndlcatfld as A only tend toward confusion and thus the present means thIQugh and lnchldlllg 1n the V is being employed to point out the various areas which in p py e 5 r fir used followed y ethylene OXIde I turn, appear in the sub-generic claims hereto appended. and this series 15 l w l 3 through i Thus, in the drawing, the area designated V corresponds tflcludlng and ly In a thlfd stirles, ethylene Q F to the area within the upper triangle the area W cone is used first followed y P p l Oxlde l ii 1s sponds to the area within the lower. triangle, the area X Indicat d as A thl'ough and lnchldltlg corresponds to that of the middle rectangle, and the areas ThlS rfilatlonshlp 13 shown In Table Y and Z correspond to those of the other rectangles.

' TABLE 111 Although the condensates are oxybutylated in a manner similar to that described above, the following exam- C r f C(gmpositiion gompmltitim (lllompglsqitilon ples are presented to illustrate the oxybutylation of the BIG OX1 95 W GT6 TO 6116 W eree ene corr s i h diifg to are mixed prior oxide l iseg hrst oxide used first condensafces' In thesaexamples ratlo and condltlon following point to oxyalkylation fglltfWed 0 followed by proxlmatlng those shown above were employed except Gt y we e pmpy fine for the use of condensate II in place of condensate I.

A A1 Ah Ac. E l B 3; e 1 g Db 3 The reaction vessel employed is a stainless steel auto- I E: clave with theiusual devices tor heating, heat control, 18 stirrer, inlet, outlet, etc., which is conventional 1n this type 5 5E: of apparatus. The capacity is approximately 4 liters. g 3 an The stirrer operatesat a speed of approximately 250 6:: Ga r.p.m. There are charged into the autoclave 500 grams Q 3% of condensate II, 300 grams of xylene and 15 grams of sodium methylate. The autoclave is sealed, swept with il l g: 5 $93: nitrogen gas and stirring started immediately and heat g gi applied. The temperature is allowed to rise to approxi- 141 V 7 mately C. At this particular'time the addition of V p t O butylene oxide is started. 7 The butylene oxide employed I In a trapa'zoid such as A B,.D, c, the area can be IS a m xture of the straight chain isomers substantially, vided conveniently 'into five portions. by fir t d i free from lsobutylene oxide.- It is added continuously at -two lines from the shorter of the two parallel'sides per- $115311 Speed that It is absorbed by the reaction a addedpendicular so as to intersect the other'longe'r parallel line 75 The amount added in thisv operation is 1500* grams. The

13 During this period the temperature is maintained at 140 C. to 155 C., using cooling water through the inner coils when necessary and otherwise applying heat it required. The maximum pressure during the reaction is 48 pounds 1 calculated the percentage of the three initial reactants for the points A,B,C',D,E,F',G',H,I and I which appear on the boundary of the 5-sided figure and also determine the five sub-divided parts of the 5-sided figure, two parts per square inch. Ignormg the xylene and sodium methy- 5 being triangles and the other being two parallelograms, late and considering only the condensate II for convenrand one tapezord. L1kew1se we have calculated the comence, the resultant product represents 3 parts by weight position for a number of examples w1th1n the area of of butylene oxide to one part by weight of condensate II. the graph and correspondlng points 1 to 18' in- The xylene present represents approximately .6 of one elusive. Note these data are included 1n Table IV 1mpart by weight. meorately following:

TABLE IV Tertiary mixture percent basis Points on bound- Conden- Butyl- Conden- Ethylnry of area, Fig. 2 sate II one sate II ene a Conden- Butyl- Ethyloxide oxide sate II ene ene oxide oxide Example 2' I Example 3' In a third step, instead of adding 1500 grams of butylene oxide, 1625 grams is added. The reaction slows up and requires approximately 6 hours, using the same operating temperatures and pressures. The ratio at the end of the third step is 9.25 parts by Weight of butylene oxide per weight of condensate 11.

Example 4' At the end of the step the autoclave is opened and an additional 5 grams of sodium methylate added, the

autoclave. flushed out as before, and the fourth and final oxyalkylation completed, using 1625 grams of butylene oxide, and the oxyalkylation is complete within 3%. hours using the same temperature range and pressure as previously. At the end of the reaction the product represents approximately 12.5 parts of butylene oxide by weight to one part of condensate II.

It is hardly necessary to point out that thisoxybutylated condensate II is subjected to oxyethylation in the same manner described above in respect to the oxyalkylation or" condensate I.

In light of what has beensaid previously, it is obvious that hardly any directions are required to produce the compounds herein specified. However, referring to the composition-10f the initial reactants based on the S- sided figure in the attached FIG. II, it will be noted we have Note the first column gives the particular point on the boundary of the 5-sided figure or Within the 5-sided figure area. Note the next three column represent the tertiary mixture which corresponds to the initial reactants, to wit, the percentages, by weight, of condensate II, butylene oxide and ethylene oxide. Thus it is apparent that one could select any particular point'and simply use the appropriate number of pounds of oxide; for instance, in

regard to point A all that would be necessary would be I to mix 5 pounds of butylene oxide with 85 pounds of ethylene oxide and use the mixture to oxyalkylate 10 pounds of condensate II. I

Similarly, in Example B, one need only mix 13.5 pounds of butylene oxide with 85 pounds of ethylene oxide and use the mixture to oxyalkylate 1.5 pounds of condensate II.

Note the fifth and sixth columns represent binary intermediate mixtures. For instance, in regard to thefvarious points on the boundary and within the S-Sidedfigure area, we have calculated the initial mixture using condensate II and butylene oxide in the first case, and using condensate II and ethylene oxide in the second case, which would be employed for subsequent oxyalkylation togive the particular composition required. Note that a binary intermediate for the preparation of point A can be prepared in any suitable manner involving 66.6 of condensate II and 33.4% of butylene oxide. Thus, for example,

. one could use 66.6 pounds of condensate II and 33.4

pounds of butylene oxide, or on a larger scale one could 1155555 55115501 condensate II and 334- pounds of butylene oxide. 4 I 9 v Referring now to the tertiary mixture table, it is apparcut that for point A condensate II and butylene oxide together represent 15%, and ethylene oxide Therefore, one could employ 15 pounds ofthe binary mixture and react itwith 85 pounds of ethylene oxide. Similarly, in regard to the fifth and sixth columns for or a mixture.

point B, the intial mixture involved condensate II and butylene oxide, representing of condensate II and 90% of butylene oxide. If desired, 10 pounds of condensate II could be reacted with 90 pounds of butylene oxide; Such mixture need only be reacted with ethylene oxide'by reacting pounds of the mixture with 85 pounds of ethylene oxide; This is obvious from the data in regard to the tertiary mixtures.

Referring now to columns 7 and 8, it is obvious and could readily produce an oxyethylated condensate II and then subject it to reaction with butylene oxide. Using this procedure in regard to A, it is obvious that the mixture represents 10.5% of condensate II and 89.5% of ethylene oxide. This product could be obtained from a binary mixture of 105 pounds of condensate II and 895 pounds of ethylene oxide. 7

Referring now to the tertiary mixture table, it is obvious that 95 pounds of such mixture could be reacted with 5 pounds of butylene oxide to give point A. Similarly, in regard to point B the oxyethylated condensate II represents 1.7% of condensate II and 98.3% ethylene oxide.

' oxyalkylations.

caustic soda, sodium methoxide, caustic potash, etc. Caustic soda is satisfactory in all the herein described As has been noted previously, it is desirable to add all the required catalyst first, i.e., enough to carry through to the very end of the oxyalkylation. This is conventional procedure; for instance, see Table I of U.S. Patent No. 2,792,369, dated May 14, 1957, to Dickson. The concentration is usually 0.14% by weight based on the finished product. .In the final stages the percentage of caustic soda present is, on a calculated basis, about 0.15%.

As has been previously noted, the pressures in allthe 7 compounds described generally come within the range of straw colored or somewhat darker.

The mixture so obtained by referring to the tertiary mixture table would be reacted with butylene oxide in the proportion of 86.5 pounds of the mixture and 13.5 pounds of butylene oxide.

Purely for purpose of illustration, we have prepared the second series butylene oxide was first used followed 7 by ethylene oxide and this series indicated as Ab, B'b,

In the first series the buthrough and including 18'b; and finally in the third I series ethylene oxide was used followed by butylene oxide and the series identified as Ac, B'c, through and includmg 18'c.

7 TABLE V Composition Composition Composition Composition corresponding where oxides are where butylene where ethylene to following mixed prior to oxide used first oxide used first point on fig. 2 oxyalkylation followed by followed by ethylene oxide butylene oxide A A'a A'b A'c. B Ba B'b Bc. O C'a 0%.. 0'0. D D'a Db Dc. E" E'a E'b E'0. F F'a. F'b Fe. G G'a- Gb G'e. H H'a- H'b Hc. I I'a- I b 1'0. .1 J'a J'b J '0. 1 1 a- 1' b 1'0. 2 2'a. '2'b 2'0. 3 3/2.. 3'b 3'0. '4 4'a 4'1) 4'0. 5' 5a 5'b 5'0. 6 6'2..- 6b 6'0. 7 7 7a- 7'1) 7'0. 8 8'a. 8'b 8'0. 9' 9'a 9' b 9'0. 10 10a 10 b 100. 11' llallb ll'c. 12' 12a 12'b 12'c. 13 13a 13'b 13'0. 14' 14a- 14 b 140. 15 l5a. 15b 150. 16 l6'a 16b 16(:. 17' 17's.. 17'b 17'0. 18 18'a.-- 18' b 18'0.

What has been said previously in regard to the tempera- ;tures used, and the amount of alkaline catalyst used applies generally to all examples. There is generally present an amount of solvent about equal to in weight or slightly less thanthe initial condensate. The final product is often diluted for convenience to give a% solution. The solvent is xylene or ahigh-boiling aromatic solvent Xylene'is advantageously used when it is desired to vacuum distill'the product so as to remove the solvent.

' .Previous reference has been made to the amount of alkaline catalyst used, whether dispersed metallic sodium t 10 to pounds per square inch.

The products obtained when the xylene evaporates resemble sticky solids or viscous liquids and are generally In some instances, this discoloration is due to contact with air while still warm and in other instances due to the fact that the solvent, instead of xylene, is a high-boiling aromatic solvent which gives some residual color. Insome instances, the

alkalinity is removed by passing CO through the mixture 7 or adding enough acetic acid to neutralize the basic material left. 7 although this could be done, for the reason that most of the uses herein described elsewhere attach no significance No particular effort is made to preserve color to color as such for use as demulsifiers for water-in-oil emulsions, as emulsifiers in cutting oils, etc.

In manyinstances, the alkali is not neutralized and the product obtained is subjected to oxyalkylation with another oxide'as, for example, an oxyethylated derivative is then subjected to reaction with propylene oxide or butylene oxide, or, inversely, an oxypropylated or oxybutylated derivative is subjected to reaction with ethylene oxide. The preferred products and particularly from the standpoint of demulsification and for many other uses involve employment of both propylene oxide and ethylene oxide, or both butylene oxide and ethylene oxide.

Previous reference has been made to the use of butylene oxide alone or in combination with either propylene oxide or ethylene oxide or, for that matter, in combination with both propylene and ethylene oxide. It is not believed anything more need be said in regard to the use of butylene For instance, note US. Patent 2,819,214, dated January 7, 1958, to De Groote et al. This is concerned with the oxyalkylation of tetra methylolcyclohexanol by use of butylene oxide and ethyl- I ene oxide in combination starting with either'one of the oxides first. Oxybutylation can be conducted in the same manner as described in this patent with specific reference to Part Two, Section 'A. Our preference in regard to the use of butylene oxide is to use it as'the initial stage, followed by oxyethylation or oxypropylation and oxyethylation. The amount preferably employed for such initial stage oxybutylation would be in the'order of equal weight or possibly twice the weight of the initial condensate. In such initial oxyalkylation employing butylene oxide, our preference againris to use a fairly high temperature to start, for instance, 120-125 C., and then drop to approximately -100 C. as previously noted. Catalyst, temperature,

' time periods, etc., are about the same as previously.

Previous referencehasbeenrmade to the useof glycide and for that matter methylglycide. Glycide (glycidol) is available from at least one source. Apparently, methylglycide is not available commercially at this time and must be prepared. Reference will be made exclusively to the .use of glycide although methylglycide, if available, would i be used in the same way. The advantage of the use of oxides employed, using for example one mole of glycide to the initial condensate, or two moles of glycide to the initial' condens'ate. :If the initial condensate has five hydroxyls, thefirst procedure would increase it to 6, and ,the' second procedure would increase it to 7 hydroxyls.

Similarly, if one oxypropylates or oxybutylates first and then adds some ethylene oxide,'it is sometimes advantageous toward the final stage of oxyethylation to add one mole of glycide for each initial hydroxyl, for instance, 3, 4, 5, 6 or 7 moles as the case may be, and then proceed with further oxyethylation. The probable result is increased branching which is of value in some instances.

BREAKING WATER-IN-OIL EMULSIONS The oxyalkylated products of the present invention can be employed in preventing breaking or resolving emulsions of the water-in-oil type, and particularly petroleum emulsions. Their use provides an economical and rapid process for resolving petroleum emulsions of the water-in-oil type, that are commonly referred to as cut oil, roily oil, emulsified oil, etc., and which comprise fine droplets of naturally-occurring waters.

One of the more advantageous aspects, of the present invention, is concerned with a process for breaking petroleum emulsions employing a demulsifier containing an oxyalkylated condensate which is derived from the condensate, propylene oxide and ethylene oxide in such Weight proportions so the average composition stated in terms of initial reactants lies approximately within the trapezoid of the accompanying drawing in which the minimum condensate content is at least 1.75% and which trapezoid is identified by the fact that its area lies within the straight lines connecting A, B, F, E. Our preference by far is to use the compositions which represent less than one-half of this total area, to wit, the smaller trapezoid A, B, D, C.

In another of its advantageous aspects, the present invention is concerned with a process for breaking petroleum emulsions, employing a demulsifier containing an oxyalkylated condensate. More specifically, said condensate is derived from carbohydrate condensates, ethylene oxide and butylene oxide in said weight proportions so that the average composition stated in terms of initial reactants lies approximately within the S-sided figure of the accompanying FIG. 11 in which the minimum condensate content is at least 1.75% and which S-sided figure is identified by the fact that its area lies within the straight lines connecting A, B, C, D and H.

Demulsification, as contemplated in the present application, includes the preventive step of commingling the demulsifier with the aqueous component which would or might subsequently become either phase of the emulsion in the absence of such precautionary measure. Simi larly, such demulsifier may be mixed with the hydrocarbon component.

These demulsifying agents employed in the treatment of oil field emulsions are used as such, or after dilution with any suitable solvent, such as water, petroleum hydrocarbons, such as benzene, toluene, xylene, tar acid oil, cresol, anthracene oil, etc. Alcohols, particularly aliphatic alcohols, such as methyl alcohol, ethyl alcohol, denatured alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol, etc., are often employed as diluents. Miscellaneous solvents, such as pine oil, carbon tetrachloride, sulfur dioxide extract obtained in the refining of petroleum, etc., are often employed as diluents. Similarly, the material or materials employed as the demulsifying agent of or process are often admixed with one or more of the solvents customarily used in connection with conventional demulsifying agents. Moreover, said material or materials are often used alone or in admixture with other suitable well-known classes of demulsifying agents.

These demulsifying agents are useful in a water-soluble form, or in an oil-soluble form, or in a form exhibiting both oil and water-solubility. Sometimes they are used in a form which exhibits relatively limited oil-solubility. However, since such reagents are frequently used in a ratio of 1 to 10,000, or 1 to 20,000, or 1 to 30,000, or even 1 to 40,000, or 1 to 50,000, as in desalting practice,

such an apparent insolubility in oil and Water is not significant, because said reagents undoubtedly have solubility within such concentrations.

In practicing our process for resolving petroleum emulsions of the Water-in-oil type, a treating agent or demulsifying agent of the kind above described is brought into contact with or caused to act upon the emulsion to be treated, in any of the various apparatus now generally used to resolve or break petroleum emulsions with a chemical reagent, the above procedure being used alone or in combination with other demulsifying procedure, such as the electrical dehydration process.

One type of procedure is to accumulate a volume of emulsified oil in a tank and conduct a batch treatment type of demulsification procedure to recover clean oil. In this procedure the emulsion is admixed with the demulsifier, for example, by agitating the tank of emulsion and slowly dripping demulsifier into the emulsion. In some cases mixing is achieved by heating the emulsion while dripping in the demulsifier, depending upon the convection currents in the emulsion to produce satisfactory admixture. In a third modification of this type of treatment, a circulating pump withdraws emulsion from, e.g. the bottom of the tank, and re-introduces it into the top of the tank, the demulsifier being added, for example, at the suction side of said circulating pump.

In second type of treating procedure, the demulsifier is introduced into the well fluids at the well-head or at some point between the well-head and the final oil storage tank, by means of an adjustable proportioning mechanism or proportioning pump. Ordinarily the flow of fluids through the subsequent lines and fittings suffices to produce the desired degree of mixture of demulsifier and emulsion, although in some instances additional mixing devices may be introduced into the flow system. In this general procedure, the system may include various mechanical devices for Withdrawing free water, separating entrained water, or accomplishing quiescent settling of the chemicalized emulsion. Heating devices may likewise be incorporated in any of the treating procedures described herein.

A third type of application (down-the-hole) of demulsifier to emulsion is to introduce the demulsifier either periodically or continuously in diluted or undiluted form into the Well and to allow it to come to the surface with the Well fluids, and then to flow the chemicalized emulsion through any desirable surface equipment, such as employed in the other treating procedures. This particular type of application is decidedly useful when the demulsifier is used in connection with acidification of calcareous oil-bearing strata, especially if suspended in or dissolved in the acid employed for acidification.

In all cases, it Will be apparent from the foregoing description, the broad process consists simply in intro ducing a relatively small proportion of demulsifier into a relatively large proportion of emulsion, admixing the chemical and emulsion either through natural flow or through special apparatus, with or without the application of heat, and allowing the mixture to stand quiescent until the desirable water content of the emulsion separates and settles from the mass.

The following is atypical installation:

A reservoir to hold the demulsifier of the kind de scribed (diluted or undiluted) is placed at the well-head where the efiluent liquids leave the well. This reservoir or container, which may vary from 5 gallons to 50 gallons for convenience, is connected to a proportioning pump which injects the demulsifier drop-wise into the fluids leaving the Well. Such chemicalized fluids pass through the flowline into a settling tank. The settling tank consists of a tank of any convenient size, for instance, one which Will hold amounts of fluid produced in 4 to 24 hours (500 barrels to 2000 barrels capacity), and in which there is a perpendicular conduit from the top of the tank to almost the very bottom so as to permit the incoming fluids to pass from the top of the settling tank to the bottom, so that such incoming fluids do not disturb Stratification which takes place during the course of demulsification. The settling tank has two outlets, one being below the water level to drain off the water resulting from demulsification or accompanying the emulsion as free water, the other being an outlet at the top to permit the passage of dehydrated oil to a second tank, being a storage tank, which holds pipeline or dehydrated oil. If desired, the conduit or pipe which serves to carry the fluids from the well to the settling tank may include a section of pipe with bafiies to serve as a mixer, to insure thorough distribution of the demulsifier throughout the fluids, or a heater for raising the temperature of the fluids to some convenient temperature, for instance, 120 to 160 F., or both heater and mixer.

Demulsification procedure is started by simply setting the pump so as to feed a comparatively large ratio of demulsifier, for instance, 15,000. As soon as a complete break or satisfactory demulsification is obtained, the pump is regulated until experience shows that the amount of demulsifier being added is just suflicient to produce clean or dehydrated oil. The amount being fed at such stage is usually 1:'10,000, 1:1'5,000, 1:20,000 or the like.

In many instances the oxyalkylated products herein specified as demulsifiers can be conveniently used without dilution. However, as previously noted, they may be diluted as desired with any suitable solvent. Selection of the solvent will vary, depending upon the solubility characteristics of the oxyalkylated product, and, of course, will be dictated in part by economic consideration, i.e. cost.

The products herein described are useful not only alone but also admixed with some other chemical demulsifier.

In recent years pipeline standards for oils have been raised so that an effective demulsifier must not only be able to break oil field emulsions underconventional conditional conditions without sludge, but a the same time it must also yield bright pipeline oil, i.e. pipeline oil that is free from minute traces of foreign matter, whether suspended Water or suspended emulsion droplets due to nonresolvable solids. In addition, the water phase should be free of oil so as not to create a disposal problem. Thus, it is presently desirable to use a demulsifier that produces absolutely bright, haze-free oil in the top layer, yields little or no interphasal sludge, and has little, if any, oil in the water phase.

For the purpose of resolving petroleum emulsions of the water-in-oil type, we prefer to employ those oxyalkylated condensates, which are obtained by the use of monoepoxides, in such manner that the derivatives so obtained have sufficient hydrophile character to meet at least the test set forth in US. Patent No. 2,499,368, dated March 7, 1950, to De Grooteand Keiser. In said patent such test for emulsification using a water-insoluble solvent, generally xylene, is described as an index of surface activity.

The above mentioned test, i.e., a conventional emulsification test, simply means that the preferred product for demulsification is soluble in a solvent having hydrophobe properties or in an oxygenated water insoluble solvent, or even in a mixture containing a fraction of a water-soluble oxygenated hydrocarbon solvent and that when shaken with water the product may remain in the non-aqueous solvent or, for that matter, it may pass into the aqueous solvent. In other words, although it is xylene soluble for example, it may also be water soluble to an equal or greater degree.

Examples The compounds listed in the following table are used to break water-in-oil emulsion. The method employed is the Bottle Test described in Treating Oil Field Emulsion, 2nd Edition, published by Petroleum Extension Service, et al., (1955), pp. 40-44. a 1

The effectiveness of the present demulsifiers is based on their ability to break oil field emulsion under conventional conditions without sludge and at the same time yield bright pipeline oil, i.e., pipeline oil that is free from the minute traces of foreign matter, whether suspended water of suspended emulsion droplets due to nonresolvable solids. A clear break is obtained. The compounds shown in Table VI are particularly effective.

TABLE VI The following compounds are particularly effective: 1a 8a 8']? 2b 9a 9'b 3b 10b 10'c 4a ll'b Ea 12b 12b Fb 14b 13'b 512 2'0 15'a 6b 4'a 16'b 7b 5'a 17'a OTHER USES AND DERIVATIVES In addition, the compounds of this invention or derivatives thereof, such as the acylated derivatives, etc., are

useful as detergents, common solvents, emulsifiers, and

the like. They may be used as emulsifying agents to emulsify or remove greases or dirt; they may be used in the manufacture of a variety of other materials such as soluble oils, insecticidal sprays, etc.

These materials are valuable as fuel oil additives and particularly when combined with a compound which has one or more basic nitrogen atoms, for instance, these compounds are particularly effective as fuel oil additives in combination with a glyoxalidine or aminoglyoxalidine.

An analogous use in which these products are equally satisfactory is that described in U.S. Patent No. 2,665,978, dated January 12, 1954, to Stayner et al. The amount employed in the same proportion or lesser amounts than referred to in US. Patent No. 2,553,183, dated May 15, 1951, to Caron et al.

Another use is for the purpose of inhibiting fogs in hydrocarbon products as described in US. Patents 2,550,981 and 2,550,982, both dated May 1, 1951 and both to Eberz. Here again, it can be used in the same proportions as herein indicated or even smaller proportions.

An additional use is where the products do not serve as an emulsifying agent alone but serve as an adjunct. Briefly stated, this last use is concerned with a coupling agent to be employed with various emulsifying agents of the kind which already appear on the market with particular reference to the fatty acid esters of oxyethylated sorbitol, sucrose, glycorol, etc. As to the use of the products herein described see The Composition and Structure of Technical Emulsions, J. H. Goodey, Royal Australian Chemical Institute Journal and Prox., vol. 16, 1949, pp. 4775. As stated, in the summary of the article it states: The technical oil-in-water emulsion is regarded as a system of four components; the dispersion medium consisting of the highly polar substance water; the disperse phase composed of hydrocarbons or other substances of comparatively-weak polarity; the coupling agent, being an oil-soluble substance involving an hydroxyl, carboxyl or similar polar group; and the emulsifying agent which is a Water-soluble substance involving an hydrocarbon radical attached to an ionizable group.

Thus, these peculiar products giving curdy precipitates with water are unusually effective as coupling agents in many instances.

These materials have particular utility in increasing the yield of an oil well by various procedures which, in essence, involve the use of fracturing of the strata by means of liquid pressure. A mixture of these products with oil or oil in combination with a gel former alone, or a gel former and finely divided mineral particles, yields a product which, when it reaches crevices in the strata which are yielding water, forms a gelatinous mass of curdy precipitate or solid or semi-solid emulsion of a high viscosity. In any event, it represents a rapid sealing agent for the strate crevices and permits pressure to be applied to fracture the strata without loss of fluid through crevices, openings or the like.

The herein described products and the derivatives thereof are particularly valuable in flooding processes for recovery of oil from subterranean oil-bearing strata when employed in the manner described in US. Patent 2,233,381 dated February 25, 1941, to De Groote and Keiser.

The products herein described are particularly effective as emulsifiers or surfactants in the preparation of drilling mud of both the aqueous type and the emulsified type. The latter type of drilling mud contains a substantial amount of hydrocarbon oil as a base and this type is sometimes referred to as oil base drilling mud.

The herein described products may be used for the resolution of oil-in-water emulsions and particularly in instances Where such emulsions contain small amounts of oil, as, for example, one-tenth of one percent or less. As a particular procedure of use one may follow What is described in US. Patent No. 2,759,607, dated August 21, 1956, to Boyd et al., or the procedure described in US. Patent No. 2,589,201, dated March 11, 1952, to Monson.

The compounds of the kind herein described may be used for the resolution or emulsions of the oil-in-water type as described in said patent to Mons-on.

These products may be reacted with alkylene imines, such as ethylene imine or propylene imine, to produce cation-active materials. Instead of an imine, one may employ what is a somewhat equivalent material, to wit, a dialkylaminoepoxypropane of the structure wherein R and R" are alkyl groups.

The products may be combined with carboxy acids, such as higher fatty acids, so as to change their characteristics or with polycarboxy acids, such is diglycolic, maleic acid, phthalic acid, succinic acid, and the like, to give resins, soft polymers, or fractional esters which are essentially monomeric. Such products and others herein described may all be used for the resolution of petroleum emulsions of the water-in-oil type. The products without further reaction are particularly valuable as additives for lubricating oils which are derived from sources other than petroleum.

Compounds of the kind herein described can be modified in regard to the hydrophobe-hydrophile balance by reaction with epoxides having 8 or more carbon atoms as, for example, the alpha-beta epoxides derived from octene, dodecene, octadacene, etc. Furthermore, they can be reacted with epoxidized fatty acids, or esters thereof, such as epoxidized butylsoyate, i.e., a butyl ester which has been derived from soya fatty acid and then reacted with a peroxide so as to introduce an epoxy ring.

The products may be reacted with acrylonitrile or the like and subsequently converted by the conventional procedure into the ammonium salt of the corresponding carboxy acid. The ammonium salt may be used as such or the free carboxy acid liberated. 7

Products of this kind may be subjected to sulfation or sulfonation as, for example, reaction with sulfamic acid, to Wit, and ammonium salt of the corresponding sulfate.

Indeed where the products have been reacted so as to introduce one or more basic nitrogen atoms as, for example, with ethylene imine or the like, such derivatives having basic nitrogen groups are effective as corrosion inhibitors and particularly for use in connection with the petroleum industry as noted in Blair and Gross Reissue Patent No. 23,227 dated May 9, 1950.

Having thus described our invention, what we claim as new and desire to obtain by Letters Patent is 1. A process of breaking a petroleum emulsion of the wat-er-in-oil type characterized by subjecting said emulsion to a demulsifying agent containing an oxyalkylated xylene-carbohydrate condensate, said condensate of xylene and carbohydrate being prepared by reacting xylene with said carbohydrate at about 40 C. to about C. in the presence of hydrogen fluoride.

A process of breaking a petroleum emulsion of the Water-in-oil type characterized by subjecting said emulsion to a demulsit'ying agent containing an oxyalkylated phenol-carbohydrate condensate, said condensate of phenol and carbohydrate being prepared by reacting phenol with said carbohydrate at about 40 C. to about 150 C. in the presence of hydrogen fluoride.

3. A process of breaking a petroleum emulsion of the water-in-oil type characterized by subjecting said emulsion to a demulsiiying agent containing oxyalkylated ldcoxy-Llaii-(o-xyly)-D-glucitol.

4%. A process of breaking a petroleum emulsion of the Water-in-oil type characterized by subjecting said emulsion to a demulsifying agent containing oxyalkylated 1- deoxy-l,l-di(p-hydroxyphenyl)D-glucitol.

5. A process of breaking a petroleum emulsion of the water-in-oil type characterized by subjecting said emulsion to a demulsifying agent containing an oxyalkylated condensate of a carbohydrate and xylene, said Oxyalkylated condensate being prepared by reacting said carbohydrate with xylene at about -40 C. to about 150 C. in the presence of hydrogen fluoride and propylene and ethylene oxides, the average composition of said oxyalkylated carbohydrate-xylene condensate in terms of initial reactants on a weight basis having a minimum carbo hydrate-xylene condensate content of at least 1.75% and lying within the straight lines of A, B, F, E of FIG- URE 1.

6. A process of breaking a petroleum emulsion of the water-in-oil type characterized by subjecting said emulsion to a demulsifying agent containing an oxyalkylated condensate of a carbohydrate and phenol, said oxyalkylated condensate being prepared by reacting said carbohydrate with phenol at about 40 C. to about 150 C. in the presence of hydrogen fluoride and propylene and ethylene oxides, the average composition of said oxyalkylated carbohydrate-phenol condensate in terms of initial reactants on a Weight basis having a minimum carbohydrate-phenol condensate content of at least 1.75% and lying Within the straight lines of A, B, F, E of FIG- URE 1,.

References Cited by the Examiner 1 UNITED STATES PATENTS De Groote et al. 252-331 A J ULIUS GREENWALD, Primary Examiner.

TQSEPH R. LTEBERMAN, ALBERT T. MEYERS,

- Examiners. u 

1. A PROCESS OF BREAKING A PETROLEUM EMULSION OF THE WATER-IN-OIL TYPE CHARACTERIZED BY SUBJECTING SAID EMULSION TO A DEMULSIFYING AGENT CONTAINING AN OXYALKYLATED XYLENE-CARBOHYDRATE CONDENSATE, SAID CONDENSATE OF XYLENE AND CARBOHYDRATE BEING PREPARED BY RECTING XYLENE WITH SAID CARBOHYDRATE AT ABOUT -40*C. TO ABOUT 150*C. IN THE PRESENCE OF HYDROGEN FLUORIDE.
 2. A PROCESS OF BREAKING A PETROLEUM EMULSION OF THE WATER-IN-OIL TYPE CHARACTERIZED BY SUBJECTING SAID EMULSION TO A DEMULSIFYING AGENT CONTAINING AN OXYALKYLATED PHENOL-CARBOHYDRATE CONDENSATE, SAID CONDENSATE OF PHENOL AND CARBOHYDRATE BEING PREPARED BY REACTING PHENOL WITH SAID CARBOHYDRATE AT ABOUT -40*C. TO ABOUT 150*C. IN THE PRESNCE OF HYDROGEN FLUORIDE. 